Continuous-wave pumped polymer laser and preparation method thereof
10879670 ยท 2020-12-29
Assignee
Inventors
Cpc classification
H01S5/12
ELECTRICITY
H01S5/1228
ELECTRICITY
International classification
H01S5/04
ELECTRICITY
H01S5/12
ELECTRICITY
Abstract
The invention provides a continuous-wave pumped polymer laser and preparation method thereof, comprising: coating an organic polymer solution onto a substrate to form an polymer film, and applying a template having a distributed feedback structure to the polymer film, or coating an organic polymer solution onto a substrate having a distributed feedback structure to form an polymer film, and applying a plate to the polymer film; heating the substrate to reach above the phase transition temperature of the organic polymer, and applying a pressure to the template or plate for 1-100 min; and cooling the substrate to reach below the phase transition temperature of the organic polymer, and removing the template or plate from the organic polymer. The method of the invention is simple, the organic polymer molecular chain and supramolecular structure are oriented to have long range order, and the obtained laser can use continuous-wave pumping.
Claims
1. A method for preparing a continuous-wave pumped polymer laser, comprising steps of: (1) coating an organic solution of an organic polymer onto a planar transparent substrate, to form an organic polymer film, and applying a template having a distributed feedback structure to the surface of the organic polymer film, or coating an organic solution of an organic polymer onto a transparent substrate having a distributed feedback structure, to form an organic polymer film, and applying a plate to the surface of the polymer film, wherein the organic polymer is a photoluminescence polymer; (2) heating the substrate to allow the temperature of the substrate to be above the phase transition temperature of the organic polymer, and then applying a pressure to the surface of the template or plate for 1-100 min; and (3) slowly cooling the substrate to allow the temperature of the substrate to be below the phase transition temperature of the organic polymer, and removing the template or plate from the surface of the organic polymer, to obtain the continuous-wave pumped polymer laser.
2. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (1), the substrate is made of silicon, silica, alumina, quartz, glass, polyamides, polyesters, polyvinylidene fluoride, polytetrafluoroethylene, or polysiloxane.
3. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (1), the organic polymer is a polyfluorene homopolymer having an emission wavelength of 400-480 nm, wherein the polyfluorene homopolymer is poly(9,9-dioctylfluorene) and/or poly(9,9-diethylhexylfluorene).
4. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (1), the organic polymer is a polyfluorene copolymer having an emission wavelength of 480-580 nm, wherein the polyfluorene copolymer is selected from the group consisting of poly(9,9-dioctylfluorene-alt-6,6-pyridine), poly(9,9-dioctylfluorene-alt-6,6-2,2-bipyridine), poly(9,9-dioctylfluorene-alt-6,6-2,2:62-terpyridine), and poly(9,9-dioctyl-alt-1-4-benzo(2,13-thiadiazole).
5. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (1), the organic polymer is a poly(phenylenevinylene) polymer having an emission wavelength of 580-700 nm, wherein the poly(phenylenevinylene) polymer is selected from the group consisting of poly[2-methoxy-5-(2-ethylhexyloxy)l,4-phenylenevinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)l,4-phenylenevinylene], and poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylacetylene].
6. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (1), the period of the distributed feedback structure matches with the emission wavelength of the organic polymer to satisfy the Bragg condition, that is 2.sub.effA=2.sub.Bragg, where .sub.eff is the refractive index of the organic polymer, A is the period of the distributed feedback structure, and .sub.Bragg is the emission wavelength of the organic polymer.
7. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the steps (2) and (3), the phase transition temperature is glass transition temperature, crystallization temperature, or order-disorder transition temperature of the liquid crystal.
8. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (2), the applied pressure is 1-100 atm.
9. The method for preparing a continuous-wave pumped polymer laser according to claim 1, wherein in the step (4), after removing the template or plate, the method further comprises the step of coating the surface of the organic polymer with a transparent protective layer, where the protective layer is made of silicon oxide, calcium oxide, polysiloxane, polyethylene terephthalate, polyethylene naphthalate, polyamide or polytetrafluoroethylene.
10. A continuous-wave pumped polymer laser prepared by the method according claim 1, comprising a transparent substrate and an organic polymer having orientation order on the transparent substrate, wherein the organic polymer is a photoluminescence polymer and has a distributed feedback structure.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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REFERENCE NUMERALS
(17) 1transparent substrate without DFB structure; 2organic polymer film; 3template with DFB structure; 4organic polymer with fixed shape; 5substrate with DFB structure; and 6plate without DFB structure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(18) The invention will be further illustrated in more detail with reference to the accompanying drawings and embodiments. It is noted that, the following embodiments only are intended for purposes of illustration, but are not intended to limit the scope of the present invention.
(19) In order to achieve a continuous-wave pumped organic optical laser of organic polymer laser, the technical solution adopted by the present invention provides methods for preparing an organic polymer DFB structure. Specifically, referring to
(20) S1. dissolving an organic polymer in an organic solvent, to prepare an organic polymer solution with a concentration of 1.0-100 mg/ml;
(21) S2. coating the organic polymer solution onto a transparent substrate without DFB structure 1, to form an organic polymer film 2 having an uniform thickness of 1-1000 nm;
(22) S3. positioning the transparent substrate without DFB structure 1 on a hot stage with the organic polymer film 2 facing upward, and positioning a template with DFB structure 3 on the surface of the organic polymer film 2, such that the surface of the template with DFB structure 3 is in contact with the surface of the organic polymer, and heating the hot stage to a temperature above the phase transition temperature of the organic polymer;
(23) S4. after the temperature of the hot stage reaches the set temperature above, applying a pressure to the template with DFB structure 3, the organic polymer film 2, and the transparent substrate without DFB structure 1, where the pressure is 1-100 atm, and the application time of pressure is 1-100 min;
(24) S5. cooling the hot stage until the temperature of the hot stage drops to below the phase transition temperature of the organic polymer, to form an organic polymer 4 with fixed shape; and
(25) S6. peeling the template with DFB structure 3 off from the surface of the organic polymer, to obtain a continuous-wave pumped polymer laser.
(26) Specifically, referring to
(27) S1. dissolving an organic polymer in an organic solvent, to prepare an organic polymer solution with a concentration of 1.0-100 mg/ml;
(28) S2. coating the organic polymer solution onto a substrate with DFB structure 5, to form a film having a thickness that is close to the height of the DFB structure;
(29) S3. positioning the substrate with DFB structure 5 on a hot stage with the organic polymer film 2 facing upward, positioning a plate with DFB structure 6 on the surface of the organic polymer film 2, and heating the hot stage to a temperature above the phase transition temperature of the organic polymer;
(30) S4. after the temperature of the hot stage reaches the set temperature above, applying a pressure to the system, where the pressure is 1-100 atm, and the application time of pressure is 1-100 min;
(31) S5. cooling the hot stage until the temperature of the hot stage drops to below the phase transition temperature of the organic polymer, to form an organic polymer 4 with fixed shape; and
(32) S6. peeling the plate without DFB structure 6 off from the surface of the organic polymer to obtain a continuous-wave pumped polymer laser, wherein the organic polymer is left in and on the surface of the substrate with DFB structure 5.
(33) The technical solution of the present invention is illustrated in combination with the following specific examples.
Example 1
(34) Poly(9,9-dioctyl-alt-1-4benzo{2,13-thiadiazole}) (F8BT) with an emission wavelength in the green region was taken as an example, the characteristic dimension of a nanoimprinting template (where the period of the DFB structure in the nanoimprinting template is 320 nm) was designed according to the Bragg diffraction equation and the emission wavelength of the organic luminescent polymer. A Bragg grating DFB structure with a width of 85 nm, a height of about 200 nm and a period of 320 nm was constructed by direct nanoimprinting. A film with a thickness of about 75 nm was obtained on a quartz substrate by spin coating, where the spin coating was carried out for 1 min at a spin speed of 5000 rpm, with a 20 mg/ml solution of F8BT in toluene). Then, the substrate with the spin-coated film was placed in a nanoimprinting machine, and covered with a nanoimprint template (planar silicon template). The temperature of the nanoimprinting system was raised to 180 C., a pressure of 60 bars was applied for 30 min. The nanoimprinting system was slowly cooled to room temperature, the pressure was removed, and the template was removed to obtain a high-fidelity F8BT Bragg grating DFB structure, which is a continuous-wave pumped polymer laser. The morphology by atomic force microscopy of the F8BT film obtained by spin coating is shown in
(35) In order to confirm its orientation order, the following methods were used for test.
(36) The molecular chain and crystal orientation in the F8BT Bragg grating obtained by the above method are analyzed by the wide-angle grazing incident X-ray diffractometer from Shanghai Synchrotron Radiation Facility. As shown in
(37) In this example, the regulation on the lifetime and luminescence quantum efficiency of singlet excitons in the orderly oriented F8BT DFB structure is tested. The specific results are as follows.
(38) The transient absorption spectrum of the orderly oriented F8BT Bragg grating is studied, as shown in
(39) In order to test the continuous-wave pumping performance of the above F8BT DFB structure, a small semiconductor laser that outputs laser as continuous light was used as a pumping light source, and the performance of the continuous-wave pumped F8BT organic polymer laser was studied by using a fiber optic spectrometer, as shown in
(40) In addition, the light output from the F8BT organic polymer laser has a distinct linear polarization characteristic. When the polarization direction of the analyzer is parallel to the direction of the F8BT Bragg grating, the intensity of the output light is the largest. When the polarization direction of the analyzer is perpendicular to the direction of the F8BT Bragg grating, the intensity of the output light is the lowest. The degree of polarization can reach 0.85. When the polarization direction of the analyzer is at an angle to the direction of the F8BT Bragg grating, the intensity of the output light can be modulated (
(41) According to this example, a film is formed on a transparent substrate by coating (for example, spin coating, spray coating, and blade coating), and a template with DFB structure is pressed into the organic polymer film under pressure. During the process, the organic polymer is heated to above the glass transition temperature, or the melting temperature or the ordered-disorder transition temperature of the liquid crystal.
(42) The above experimental results show that the organic polymer DFB structure with orderly oriented molecular chain and crystal constructed by this method shows anisotropy or dichroism in the information of aggregation structure of the organic polymer obtained by a scattering method or by spectroscopy.
(43) The organic polymer DFB structure with increased molecular conjugation length constructed by this method has red shifted peak position in the absorption spectrum or luminescence spectrum of the organic polymer DFB structure, compared with the film or solution.
(44) The continuous-wave pumped organic optical laser achieved by this method not only utilizes continuous light pumping, but also outputs continuous light. In addition, the light output from the organic polymer laser prepared by the method also has polarization characteristics.
Example 2
(45) poly(9,9-dioctylfluorene) (PFO) with an emission wavelength in the blue region was taken as an example, the characteristic dimension of a nanoimprinting template (where the period of the DFB structure in the nanoimprinting template is 280 nm) was designed according to the Bragg diffraction equation and the emission wavelength of the organic luminescent polymer. A Bragg grating DFB structure with a width of 100 nm, a height of about 200 nm and a period of 280 nm was constructed by direct nanoimprinting. A film with a thickness of about 75 nm was obtained on a quartz substrate by spin coating, where the spin coating was carried out for 1 min at a spin speed of 4000 rpm, with a 15 mg/ml solution of PFO in toluene). Then, the substrate with the spin-coated film was placed in a nanoimprinting machine, and covered with a nanoimprint template (planar silicon template). The temperature of the nanoimprinting system was raised to 180 C., a pressure of 60 bars was applied for 5 min. The nanoimprinting system was slowly cooled to room temperature, the pressure was removed, and the template was removed to obtain a high-fidelity PFO Bragg grating DFB structure, which is a continuous-wave pumped polymer laser. The scanning electron micrographs of the cross-section and surface of the PFO Bragg DFB structure are shown in
(46) In order to confirm its orientation order, the following methods were used for test.
(47) The molecular chain and crystal orientation in the PFO Bragg grating obtained by the above method are analyzed by the wide-angle grazing incident X-ray diffractometer from Shanghai Synchrotron Radiation Facility. As shown in
(48) In order to test the continuous-wave pumping performance of the above PFO Bragg DFB grating, a small semiconductor laser that outputs laser as continuous light is used as a pumping light source, and the performance of the continuous-wave pumped PFO organic polymer laser is studied by using a fiber optic spectrometer, as shown in
(49) In addition, the light output from the PFO organic polymer laser has a distinct linear polarization characteristic, as shown in
(50) The above experimental results show that the organic polymer DFB structure with orderly oriented molecular chain and crystal constructed by the method of the present invention shows anisotropy or dichroism in the information of aggregation structure of the organic polymer obtained by a scattering method or by spectroscopy.
(51) The continuous-wave pumped organic optical laser achieved by this method not only utilizes continuous light pumping, but also outputs continuous light. In addition, the light output from the organic polymer laser prepared by the method also has polarization characteristics.
Example 3
(52) poly(9,9-dioctyl-alt-1-4benzo{2,13-thiadiazole}) (F8BT) with an emission wavelength in the green region was take as an example, the characteristic dimension of a nanoimprinting template (where the period in the nanoimprinting template is 320 nm) is designed according to the Bragg diffraction equation and the emission wavelength of the organic luminescent polymer. Bragg grating DFB structures with a width of 85 nm, 95 nm, 110 nm, 135 nm, 180 nm, and 200 nm respectively, a height of about 200 nm and a period of 320 nm were constructed by direct nanoimprinting. For the specific method, refer to Example 1. A high fidelity F8BT Bragg grating DFB structure can be obtained. as shown in
(53) The molecular backbone orientation of F8BT nanostructure arrays can be quantitatively characterized by polarized ultraviolet absorption spectroscopy and polarized fluorescence spectroscopy.
(54) The regulation on the lifetime and luminescence quantum efficiency of singlet excitons in various orderly oriented F8BT DFB structures prepared in this example is tested. The specific results are as follows.
(55) The transient absorption spectrum of the orderly oriented F8BT Bragg grating is studied, as shown in
(56) In order to test the continuous-wave pumping performance of the above F8BT DFB structure, a small semiconductor laser that outputs laser as continuous light was used as a pumping light source, and the performances of the continuous-wave pumped F8BT organic polymer lasers having the same period, but different sizes of DFB structure were studied by using a fiber optic spectrometer. A small semiconductor laser that outputs laser as continuous light is used as a pumping light source, and the performance of the continuous-wave pumped F8BT organic polymer laser was studied by using a fiber optic spectrometer, as shown in
(57) In addition, the light output from the F8BT organic polymer laser has a distinct linear polarization characteristic. When the polarization direction of the analyzer is parallel to the direction of the F8BT Bragg grating, the intensity of the output light is the largest. When the polarization direction of the analyzer is perpendicular to the direction of the F8BT Bragg grating, the intensity of the output light is the lowest. The degree of polarization can reach 0.85, and the degree of polarization gradually decreases as the characteristic dimension of the Bragg grating increases. In summary, the laser performance (threshold, degree of polarization) can be successfully modulated by modulating the characteristic dimension of the Bragg grating.
Example 4
(58) Poly(9,9-dioctylfluorene) (PFO) with an emission wavelength in the blue region was taken as an example, the characteristic dimension of a nanoimprinting template (where the period in the nanoimprinting template is 280 nm, and the width is 100 nm, 140 nm, and 160 nm respectively) was designed according the Bragg diffraction equation and the emission wavelength of the organic luminescent polymer. Bragg grating DFB structures with a width of 100 nm, 140 nm, and 160 nm, a height of about 100 nm and a period of 280 nm were constructed by direct nanoimprinting. For the specific method, refer to Example 2. A continuous-wave pumped polymer laser can be obtained.
(59) The molecular backbone orientation of PFO nanostructure arrays can be quantitatively characterized by polarized ultraviolet absorption spectroscopy.
(60) In order to test the continuous-wave pumping performance of the above PFO DFB structure, a small semiconductor laser that outputs laser as continuous light is used as a pumping source, and the performance of the continuous-wave pumped PFO organic polymer laser is studied by using a fiber optic spectrometer, as shown in
(61) In addition, the light output from the PFO organic polymer laser has a distinct linear polarization characteristic, as shown in
(62) The above experimental results show that the organic polymer DFB structure with orderly oriented molecular chain and crystal constructed by the method of the present invention shows anisotropy or dichroism in the information of aggregation structure of the organic polymer obtained by a scattering method or by spectroscopy, and the orientation order of the molecules and crystals can be regulated by the DFB structures with the same period, but different sizes.
(63) By using the DFB structures with the same period, but different sizes constructed by this method, the degree of long-range order of the polymer molecules and crystals decreases as the width increases.
(64) The laser performance of the continuous-wave pumped organic polymer laser achieved by the method can be adjusted by the characteristic dimension of the DFB structure.
(65) The above description is only preferred embodiments of the present invention and not intended to limit the present invention, it should be noted that those of ordinary skill in the art can further make various modifications and variations without departing from the technical principles of the present invention, and these modifications and variations also should be considered to be within the scope of protection of the present invention.